Vinyl chloride polymers plasticized with morpholides of fatty acids and dimerized fatty acids



July 12', 1966 F. c. MAGNE ETAL 3,260,692 7 E POLYMERS PLASTICIZED WITH MORPHOLIDES Y ACIDS AND DIMERIZED FATTY ACIDS Filed Feb. 19. 1965 VINYL CHLORID 0F FATT A \9 2O AVAVYQ, MINA United States Patent 3 260,692 VINYL CHLORIDE POLYMERS PLASTICIZED WITH MORPHOLIDES 0F FATTY ACIDS AND DIMERIZED FATTY ACIDS Frank C. Magne, Evald L. Skau, and Robert R. Mod, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture Filed Feb. 19, 1963, Ser. No. 260,100 5 Claims. (Cl. 260-30.4)

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This application is a continuation-in-part of application bearing Serial No. 166,742, filed January 15, 1962, now Patent No. 3,219,664 and entitled Vinyl Chloride Polymers Plasticized with Morpholides.

This invention relates to unique morpholides. More particularly, the invention provides the morpholides of mixtures of long chain saturated and unsaturated fatty acids and the epoxy and dimer derivatives thereof that can reproducibly be produced from the fatty acids found in natural glycerides. These mixed morpholides are efficient primary solvent plasticizers exhibiting good compatibility with homopolymers and copolyrners of vinyl chloride. 6

A morpholide of an acid is an amide of the acid in which the amide nitrogen atom is a nitrogen atom of a morpholiue ring. Prior workers have produced the morpholides and other amides of various individual fatty acids and mixtures of fatty acids. Many of the fatty acid amides heretofore produced, e.g., those disclosed in US. Patents 1,986,854; 2,339,056; and 2,380,925; are solvent plasticizers for hydrophilic vinyl resins such as the polyvinyl acetal resins.

, A. compound which is a solvent plasticizer for, and thus .is compatible with, a hydrophilic vinyl resin such as a polyvinyl acetal resin, exhibits only a very limited comp'atibility with a hydrophobic vinyl resin such as polyvinyl chloride. If a resin is plasticized with a compound with which it has only a limited compatibility the plasticizer soon exudes or migrates to the surface unless the plasticizer is used in limited amount, or is used in conjunction with a mutual solvent, to obtain adequate compatibility.

As might be expected from the known compatibility of various morpholides of fatty acids with the polyvinyl acetals, the morpholide mixtures from glyceride oil acids such as cottonseed oil acids or peanut oil acids, although in other respects satisfactory vinyl chloride resin plasticizers, are highly incompatable with polymers of vinyl chloride, even when used as a secondary plasticizer with an equal amount of a highly compatible plasticizer.

Similarly, the morpholide of palmitic acid and the morpholide of stea-ric acid, though in other respects satisfactory vinyl chloride plasticizers, have been found to be highly incompatible when used as plasticizers for vinyl chloride resins, exhibiting migration to the surface within 36 hours.

The term vinyl chloride resins is used throughout the specification andclaims to refer to homopolymers "and copolyrners of monomers containing vinyl chloride 3,250,692 Patented July 12, 1966 "ice in a predominant proportion in parts by weight. Terms such as good compatibility, compatible, and compatible plasticizers in reference to plasticizers for vinyl chloride resins are used throughout the specification to refer to plasticizers which show no signs of exudation or migration to the surface for at least 30 days when the plasticizer is present in the proportion of about parts per parts by weight of' vinyl chloride resin.

The primary object of the present invention is to provide morpholides which are good primary solvent plasticizers for vinyl chloride resins, and which are plasticizers that can economically be produced from fatty acids obtainable from glyceridic oils and fats.

The morpholides provided by this invention exhibit good compatibility with homopolymers and copolyrners of monomers predominating in vinyl chloride, such as polyvinyl chloride, and the vinyl chloride-vinyl acetate copolyrners predominating in vinyl chloride. They may be employed as plasticizers in proportions of from 10 to about 70 parts by weight per 100 parts by weight of polymer. Their plasticizing efficiency is high and the resulting plasticized resins have good thermal and light stability, good low-temperature properties, and a low volatility loss.

In US. Patent No. 2,863,845 it was disclosed that the morpholides of mixed saturated and unsaturated vegetable oil fatty acids in which mixtures of acids, the weight proportions of saturated acids (S), monoolefinic acids (M), polyolefinic acid-s (P), and epoxidized fatty acids (E), are such that S/S+M+P+E is from about 1 to 9/100 and P/M-l-P-t-E is less than about l/10, the value of B being zero when no epoxidized fatty acids are present in the fatty acid mixture, are good compatible plasticizers for vinyl chloride resins. The term epoxidized fatty acids is used to designate C to C alkanoic and alkenoic acids containing at least one epoxy group. Such acids are produced by the epoxidation of at least one olefinic group of an unsaturated fatty acid.

Terms such as dimer acids, dimer acid, or dimerized acids are used indiscriminately to refer to acids or mixtures of acids consisting essentially of dibasic acids containing from 32 to 44 carbon atoms resulting from the polymerization or dimerization of long chain C to C unsaturated fatty acids. The term dimerized cottonseed fatty acids is used to refer to cottonseed fatty acids which have been subjected to dimerizing treatment.

In copending patent application Serial No. 79,470 filed December 29, 1960, now Patent No. 3,066,111, it was further disclosed that the morpholide mixtures obtained by reacting morpholiue with mixtures of the fatty acids which occur in selectively hydrogenated cottonseed oil, said morpholide mixtures containing a proportion of saturated, monounsaturated, and polyunsaturated acyls; i.e., acyls obtainable from selectively hydrogenated cottonseed oil, such that the acyls are equivalent to a mixture of acids in which S/S-l-M-l-P is about 25/100 and P/ M +P is less than 1/ 10, are good compatible plasticizers for vinyl chloride resins.

We have now made the surprising discovery that mixtures of morpholides of vegetable oil fatty acids containing a proportion of saturated, monounsaturated, and polyunsaturated acyls such that the acyl mixture is equivalent -to a mixture of acids in which P/M-i-P is much larger than 1/10 are compatible plasticizers for vinyl than about 17% of all the acyls in This is surprising since, as is obvious such compatible plasticizing mixtures the morpholide. from the drawing, can be prepared by of all the acyls in the morpholide mixture. This is surprising since it shows, as can be seen from the drawing, that compatible tively.

than about 17% of all the acyls in the morpholide mixture. For example, the composition represented by Example 43, for which P/M+P+E= about 35/100 and the composition represented by Example 40, for which S/S+M+P+E= about 75/100 are individually incompatible, but a mixture of equal parts of these compositions (Example 46), for which E/E+S=54/100 and E/P+E=72/100 is compatible.

acids (S), and polyolefinic acids (P), are such that the following conditions are satisfied: (1) that S/S-f-P is greater than about 50/100 (i.e., that the composition lies within area Mes in the drawing), (2) that M/S+M+P is greater than about 30/100 i.e., that the composition lies within P/M+P are such that the following condigenation, epoxidation, etc., and/or (3) by admixing with other fatty acid mixtures 'and/ or with pure fatty acids. Alternatively, the fractionation, hydrogenation, epoxidation or mixing,

as determined by standard analytical procedures. For example, consider a mixture of vegetable oil fatty acids in which the weight proportions are such that S/S+P is about 35/100; P/M+P is about 65/100; M/S+M+P is about 25/100; and in which the predominant saturated fatty acid is the C acid with very small amounts of the C and C acids.

--overall composition The drawing shows that the mixed morpholides made from this mixture (represented approximately by w in the drawing) would be incompatible. The drawing also shows that this mixture of fatty acids can be readily converted to .a suitable mixture of acids (i.e., to a composition represented by points within area Mfgc), which when reacted with morpholine will result in a compatible plasticizer; for example, by converting some or all of the polyunsaturated acyls to monounsaturated acyls by such procedures as hydrogenation, halogenation, rformylation, dimerization, maleination, etc., so that S/S-l-P is greater than about 50/100, M/S+M+P is greater than about 30/100, and P/M+P is less than about 40/ 100.

The composition of the morpholide mixtures of this invention which contain no epoxidized acyls are represented by all compositions within the area Mfgc in the drawing; that is, within the area bounded approximately by Mf, fg, and go. The boundaries Mf, fg, and go are only approximate. Thus the composition of Example which lies near the boundary outside this area is compatible. Slightly incompatible compositions lying close to but outside the boundaries M1, fg, and go and even less compatible compositions may be used satisfactory as primary plasticizers in polyvinyl chloride resin formulations containing lower percentages of plasticizer and/or as secondary plasticizers admixed-with a suitable compatibilzing plasticizer such as the morpholide of epoxidized fatty acids or compatible mixtures of the morpholides of epoxidized fatty acids and/or monounsaturated fatty acids and/ or polyunsaturated fatty acids and/or saturated fatty acids. Similarly incompatible morpholide mixtures containing the morpholidesxof epoxidized fatty acids can be used as secondary plasticizers with compatible morpholide compositions which lie within the area Mfgc in the drawing.

The proportion of the saturated fatty acyls having 18 or more carbon atoms in the chain which can be present in the saturated acyl fraction without causing incompatibility will vary vvith the overall composition of the morpholide mixture, particularly the relative proportions of saturated, monounsaturated, and polyunsaturated acyls present in the mixture. It can be determined for a given by evaluating the'perf-or-mance of a series of samples which differ only in the proportion of the C or longer-chain saturated fatty acyls in the saturated fatty acyls present.

We have also discovered that the morpholides of epoxidized fatty acids, i.e., of C to C alkanoic or alkenoic acids containing at least one epoxy group, are compatible, highly efficient, primary plasticizers for vinyl chloride resins and impart to the plasticized resin a high degree of stability against heat and light. They are efficient stabilizers for vinyl chloride resins. We have also discovered that morpholide mixtures such as can be made by mixing even as much as about one part of the morpholide of palmitic acid with one part of the morpholide of epoxidized fatty acids or by mixing as much as about 3 parts of the morpholide of polyunsaturated fatty acids with 7 parts of the morpholide of epoxidized fatty acids are also compatible vinyl chloride resin plasticizers and have the advantage that the plasticized resin has increased thermal stability.

Morpholide mixtures which can be prepared by mixing in any proportion any of the compatible morpholide compositions w-it-hin the area Mfgc in the ClIlEllWll'lg with either the morpholides of epoxidized fatty acids or with any mixture of morpholides of fatty acids containing the morpholide of epoxidized fatty acids which mixture of morpholides is itself a compatible vinyl chloride plasticizer are also compatible vinyl chloride plasticizers imparting good thermal stability to the resin. In making such compatible morpholide mixtures the morpholides of epoxidized fatty acids may beintroduced by addition or they may be formed in situ', for example, by epoxidizing some of the v of morpholides 6 the monounsaturated or polyunsaturated fatty acids in a given morpholide mixture.

We have also discovered that the morpholides of dimer acids are compatible, eflicient, and permanent primary plasticizers for vinyl chloride resins and that the molded resins plasticized with such morpholides show .a surprisingly low volatility loss. More surprising is the fact that essentially zero volatility losses are also obtained when the dimer acid morpholide is mixed with its own weight of another plasticizer which plasticizer when used alone would impart a moderately high volatility loss. The morpholide of dimer acids can therefore be used in conjunction with other more volatile plasticizers to eliminate or reduce volatility loss.

Conversely a particular plasticizing property of the morpholides of dimer acids, such as. low-temperature properties, can be improved by using said morpholides in admixture. with other appropriate plasticizers which excel morpholides of i in this property. Improved light stability and thermal stability can be attained by inclusion of suitable stabilizers and/or antioxidants in the resin-plasticizer. formulation.

Vinyl chloride resins plasticized with the morpholides of dimer acids also exhibit the desirable property of low soapy water extractability. They are also useful for reducing the soapy Water extractability of other more highly extractable. plasticizers when used in admixture with such plasticizers.

We have also discovered that pholide of dimer acids (MD), acid (MO), and the morpholide in which the weight fraction of 0.55 and also those mixtures in which the weight fraction of MO is greater than 0.10, and the weight .fraction of MP is between 0.55 and about 0.70, are compatible plasticizers the more important plasticizing characteristics of which can be predicted approximately from those of the individual morpholides and their weight proportions in the given mixture.

.Morpholide mixtures which can be prepared by mixing in any proportion any compatible morpholide mixture containing the morpholide of dimer acids with either the morpholide of epoxidized fatty acids or with any mixture of fatty acids containing the morpholide of epoxidized fatty acids which mixture of fatty acids is itself a compatible vinyl chloride plasticizer are also compatible vinyl chloride plasticizers impartinggood thermal stability to the resin.

The following examples numbered 1 through 68, the data for which are listed singly in tabular form but which may be considered individually or in related groups for discussion purposes, will demonstrate several of the manifold expressions of our invention.

Various morpholide mixtures were tested as plasticizers for vinyl chloride-vinyl acetate (-5) copolymer resin (Vinylite VYDR) in a standard formulation comprising: 63.5% of Vinylite VYDR, 35% plasticizer, 0.5% stearic acid, and 1.0% basic lead carbonate. This formulation for each morpholide sample was milled, molded, and tested. In all examples, the sample was rated as incompatible if the molded stock showed any evidence of exudation or migration to the surface during a shelf storage of 30 days.

The morpholide mixtures used in Examples 1 to 19 were ternary compositions prepared by mixing appropriate proportions of the morpholide of oleic acid, the morpholide of linoleic acid, and the morpholide of palmitic acid. The approximate compositions and the results of the compatability test for these samples are given in Table I and plotted as points in the ternary weight-composition diagram in the sole figure of the drawing. In this figure compatible morpholide mixtures are represented by open circles and incompatible mixtures by black circles. In Table I, M, S, and P represent the weight percent of the morpholides of oleic, palmitic, and linoleic acids comprising the morpholide mixture, respectively.

all mixtures of the morthe morpholide of oleic of palmitic acid (MP), MP is less than about TABLE I Example N o.

60. 5 38. 1 1. 3 61/100 2/100 97/100 C 51. 2 47. 7 1. 1 51/100 2/100 98/100 C 78. 6 14. 5 6. 8 79/100 8/100 68/100 C 71. 4 19. 2 9. 3 71/10 12/100 67/100 C 80. 7 9. 8 9. 5 81/100 11/100 51/100 C 37. 2 61. 9 0. 8 37/100 2/100 99/100 C 45. 38. 4 16. 5 45/100 27/100 70/100 C 45. 5 42. 0 12. 3 46/100 21/100 77/100 C 35. 1 43. 2 21. 5 35/100 38/100 67/100 C 26. 3 67. 4 16. 1 26/100 38/100 78/100 0 53. 8 24. 2 21. 9 54/100 29/100 52/100 C 63. 6 19. 3 16. 9 64/100 21/100 53/100 0 70. 0 11. 2 18. 8 70/100 21/1 37/100 I 70. 0 15. 0 15. 0 70/100 18/100 50/100 0 43. 4 36. 0 20. 6 43/100 32/100 64/100 C 45. 3 40. 1 14. 6 45/100 24/100 73/100 C 40. 5 30. 0 29. 5 41/100 42/100 50/100 I M, S, P. MIS+M+P P/M+P S/S-I-P Compatpercent percent percent ibility 1 25/100 2/100 99/100 1 0=Compatible; I=Incompatible.

The sample used in Example 20 was the morpholide of animal type acids, that is, a mixture of fatty acids having the following composition: 10% myristic, 43% palmitic, 9% stearic, 30% oleic, and 8% linoleic acids.

ich consisted of approximately 9.6% linolenic acid, 13.3% linoleic acid, 20.4% oleic acid, 49%

P/M+P= about 0 and S/S+P= about 100/100, resulting in a final mixture for which M/S+M+P= about 72/100,'P/M+P= about 14/100 and S/S+P= about 59/100. This was found to be a compatible plasticizer for Vinylite VYDR resin.

The compositional data for of Examples to 23 are given in Table II in which Table, M, S, and P, morpholides of monoolefinic, saturated and polyolefinic fatty acids, respectively, comprising the morpholide mixture, in which morpholide mixture, the saturated acyls containing 18 or more carbon atoms amount to less than about 17% of all the acyls in the morpholide mixture.

TABLE II Example M, Wt. S, Wt. P, Wt. M/S+M+P P/M-l-P SIS+P Compat- N 0. percent; percent percent ibility 1 erucic acid, and 7.6% saturated fatty "acid. The resulting morpholide mixture, for Which the composition was such that M/S+M+P=69/100, P/M+P=/100, and

' TABLE III Example Plasticizer, Morpho- Tensile 100% Elonga- Brittle Compati- N o. lide of- Strength, Modulus,

20 Animal type acids 21 Animal acids 22 Rapeseed oil acids 23 Adjusted rapeseed oil acids. 24- Epoxyoleic acid 25 Epoxystearic acid 26 Diepoxystearic acid 27 Partially expoidized cottonseed oil acids. 28 Fully epoxidized cottonseed oil S/S+P=25/ 100, was tested as a plasticizer for VYDR resin and was incompatible.

Vinylite 6 69 25/ 25/10 3 72/100 14/100 59/100 1 C Compatible; I=Incompatible.

ticlzed with the morpholide mixtures of Examples 20 to 23 are shown in Table III.

tron, P oicnt, Volatility bility p.s.1. p.s.1. percent 2, 940 1, 390 400 30 0. 62 C 2, 950 1, 370 390 34 0. 36 C 3, 030 1, 470 400 53 1. 00 I 2, 880 330 360 43 0. 55 O 3, 030 1, 270 360 16 0. 41 C 2, 850 1, 300 350 28 0. 54 C 2, 950 1, 330 350 16 0. 49 C 2, 940 1, 210 400 26 0. 73 C atoms amount-to'lessthan about 17% of all-the acyls in the morpholide mixture. The morpholide samples of Examples 24 and'26 were'prepared from the morpholide of linoleic acid and that for Example 25 from the morpholide of oleic acid by epoxidization with perbenzoic or peracetic acid. The morpholide-samples of Examples 27 and 28 were prepared by epoxidation of the morpholide anhydrous sodium-sulfate. Free acid was removed by percolating the hexane solution through a column of activated alumina and eluting the morpholide with a 1:1 hexane-ethanol mixture. The solvent was removed by stripping under reduced pressure. The product was acidfree and had a nitrogen content of 3.87%.

The sample used in Example 48 was the morpholide of cottonseed oil fatty' acids to an oxirane content of of a trimer-free dimer ac d. The morpholide was prepared 2.62% and 4.07%; i.e.,,to an extent equivalent to that by the same procedure as described in Example 47. necessary to epoxidize about 40% and about 100%, re- 10 The product was acid-free and had a nitrogen content spectively, of the total number of double bonds present. of 3.90%.

TABLE IV M E s P E/E-l-S E/P-l-E Compatibility 100 0 o o 100 0 o o 100 0 o 25 50 25 0 0 75 25 o '51 21 o 0 50 40 o o 55 45 o 0 45 55 r 30 50 c 17.7 26.8 55.5 0 15 p 23 52 o 12 is 70 o 40 50 r .35 65 I 30 70 r 25 75 I 0 o 0 o o I 37. o 37. o 57. 0

2 Compositions containing the morpholides of both monounsaturated fatty acids and be prepared by mixing appropriate proportions of two morpholide mixtures each of which is a compatible vinyl chloride plasticizer.

both monounsaturated fatty acids and and 75 parts of the morpholide of palmitic acid and the other consisting of For example the sample of by weight of two incompatible morof a monounsaturated acid parts of the morpholide 0i epoxyoleic acid and 65 parts of the morpholide of palmitic acid.

The morpholide sample. of Example 29 was prepared by -mixing the proper proportions of the morpholide mixture of Example 28 and the morpholide of selectively hydrogenated cottonseed fatty acids. The plasticized resin had a specially. high degree of thermal stability.

The morpholidemixtures used in Examples 30 to 36, for 'whichthe compatibility. data are given in Table IV, were preparedrby mixing the proper proportions of the ,morpholides of oleic acid, epoxyoleic acid, and palmitic acid.

The morpholide mixtures used in Examples 37, 38, 39, 40, 41, 42, and 43 were binary compositions'prepared by mixing appropriate proportions of the morpholide ofv epoxyoleic acid with either the morpholide of linoleic acid or with the morpholide of palmitic acid. The morpholide mixtures used in Examples 44, 45, and 46 were ternary mixtures consisting of equal parts by weight of the mixture used in Example and those used in Examples 41, 42, and .43, respectively. The compositions and the results of the compatibility tests for these samples are givenin Table IV. The sample of Example 46 was acompatible vinyl chloride. plasticizer though it was made by mixing the samplesof Examples 40 and 43. both of which were. incompatible.

The sample of Example 47 was the morpholide of the mixture of acids comprising about 75% of dimer acid, 22% of trimer acid, and 3% of monomer. The morpholide was prepared by refluxing the acids with an excess of morpholine in an. apparatus equipped with a Dean-Stark trap until the evolution of water ceased, using benzene as the entraining liquid. The reaction mixture was taken up in commercial hexane, washed successively with dilute hydrochloric acid and water, and dried over -The samples of Examples49, 50, and 51 were prepared by mixing the proper proportions of the morpholide of Example 47 and the morpholide of a fatty acid mixture which mixture of fatty acids was prepared by saponification and acidulation of a cottonseed oil which had been selectively hydrogenated to an iodine value of 70.3 and a thiocyanogen value of 64.6.

The sample of Example 52 was prepared from cottonseed fatty acids which had been subjected to a dimerization treatment. A 46.5-gram sample of cottonseed fatty acids, 1.5 grams of water, and 2.0 grams of activated bleaching clay were placed in a flask equipped with a stirrer and reflux condenser. The mixture was heated at 230 C. for 4 hours, taken up in 50 ml. of commercial hexane, and filtered to remove the bleaching earth. The hexane was removed by stripping under reduced pressure. The product, dimerized cottonseed acids, had a neutralization equivalent of 303. It was condensed with morpholine to form the morpholide of dimerized cottonseed acids by the procedure described in Example 47. The product was acid-free and had'a nitrogen content of 3.66%.

The physical properties of the Vinylite VYDR resin plasticized with the morpholides of Examples 47 to 52 are shown in Table V. The volatility losses were determined by the activated carbon method ASTM-D1203- 52T.

The morpholide mixtures used in Examples'53 to 68 include binary and ternary compositions prepared by mixing appropriate proportions of the morpholide of the dimer acid used in Example 47, the morpholide of oleic acid, and the morpholide of palmitic acid. The compositions and the results of the plasticizer evaluation tests for these samples are given in Table VI. In Table VI, MD, MO, and MP represent the weight percent of seed oil that has been selectively hydrogenated to reduce the monpholides of dimer, oleic, and palmitic acids comsubstantially all the polyunsaturates to monounsaturates, prising the mixture, respectively. the total amount of saturates being maintained essen- TAB LE V 503.133 Example Tensile 100% Elonga- Brittle Volatility Water Ex- Compati- No. Plasticizer Strength, Modulus, tion, Per- Point, 0. Loss, tractabilbility l p.s.i. p.s.i. cent Percent ity, Percent Morpholide of Dimer Acid (mixed with trimer and monomer) 3, 670 2, 870 300 +3 0 2. 3 O Morpholide of Dimer Acid (trimet-free) 3, 430 2, 870 260 +3 0. 0 C Hyd C/S Morpholide-l-Dimer Morpholide (1-3) 3, 490 2, 300 340 9 0. 0 5. 4 O Hyd C/S Morpholide+Dimer Morpholide (ll) 3, 220 1, 890 300 21 0. 0 9. 0 C Hyd O/S Morpholide-l-Dimer Morpholide (3-1)- 3, 090 1, 670 320 31 0. 41 13. C Morpholide of Dimerized O/S Aolds 2, 960 1, 590 360 29 C 1 C Compatible.

TABLE VI Tensile 100% Elongation, Brittle Example N 0. MD, percent M0, percent MP, percent Strength, Modulus, percent Point, C. Compatibility p.s.1. p.s.1. M a 0. 0 50. 0 50. 0 2, 880 1, 310 390 -33 G 5. O 90. O 5. 0 2, 970 1, 410 370 37 C 12. 5 75. O 12. 5 2, 970 1, 450 400 33 O 12. 5 12. 5 75. 0 2, 780 1, 350 340 I 25. 0 56. 25 18. 75 3,080 1, 5 70 320 -31 C 25. O 37. 5 37. 5 3, 070 1, 5 00 380 27 C 25. 0 50. 0 25. 0 3, 120 1, l 80 370 29 C 25. O 25. 0 50. 0 3, 190 1, t 60 380 25 C 32. 5 32. 5 35. 0 3, 120 1, C 40 400 23 C 50. 0 50. O O. 0 3, 308 1, 262 375 -19 C 50. 0 25.0 25.0 3, 240 1, E 30 400 19 O 50. 0 37. 5 12. 5 I 3, 220 1, S 90 300 21 C 50. 0 0. 0 50. 0 3, 280 1, 930 360 13 C 75. 0 12. 5 12. 5 3, 400 2, 320 310 -7 O 75. 0 18. 75 6. 25 3, 490 2, 290 330 9 C 0. 0 0. 0 100. 0 2, 530 1, 270 340 -27 I 1 O Compatible: I =Incompatible.

We claim: tially unchanged, said morpholides of the dimerized long 1. A plastic composition consisting essentially of a mixchain fatty acids and said morpholides of the selectively ture containing a vinyl chloride polymer selected from the hydrogenated cottonseed fatty acids being present in the group consisting of polyvinyl chloride and .a vinyl chlomorpholide mixture in the ratio of.about from 1 to 3 amount of vinyl chloride, and from 10% to 70% by weight of e latter.

based on the weight of the polymer of a plasticizer com- 4. A plastic composition consisting essentially of a mixprising a mixture of morpholides of dimerized long chain ture Containing 51 Vinyl Chloride P y SeleCted ffOm the fatty acids which acids consistessentially of dibasrc acids containing from 32-44 carbon atoms and WhlCll d1bas1c ride-vinyl acetate copolymer whlch contams a p ac1ds result from the dlmerizatlon of (3 to C22 unsatunant amount of y chlon'de, and f m 10% t 70% rated fatty id by Weight based on the weight of the polymer of a plas- 2. A plastic composition consisting essentially of a mixficizel' comprising a mixture of morpholides 0f Oleic acid ture containing .a vinyl chloride polymer selected from 55 p m ac d (MP), and dimer acids (MD), which the group consisting of polyvinyl chloride and a vinyl dimer acids consist essentially of dibaslc ac1ds containing chloride-vinyl acetate copolymer which contains prefrom 32-44 carbon atoms resulting from the dimerization dominant amount of vinyl chloride, and from 10% to of C16 150 C22 unsaturated fatty acids, Said plasticizer C 70% by weight based on the weight of the polymer of a prising any miXtufe of said morphohdes containing at plasticizer comprising a mixture of morpholides of dimerized cottonseed oil fatty acids.

3. A plastic composition consisting essentially of a p fli cOIIIPP'SitiOII collsisting essentially of amiX- mixture containing a vinyl chloride polymer selected from ture contammg Vlnyl chlonde Polymer Selected ffOm the group consisting of polyvinyl chloride and a vinyl 6 group conslstmg of Polyvmyl chlonde and a Vlnyl chloridem-nyl acetate copolymer which contains a chloride-vinyl acetate copolymer which contains a precizercomprising a mixture of morpholides of oleic (MO), palmitic acid (MP) and dimer acid (MD), which dimer tially of dibasic acids containing from 32-44 carbon atoms 32 44 cal-b selectively hydrogenated cottonseed fatty acids which least 10 weight percent of M0, at least 20 weight perm-orphohdes of selectively hydrogenated cottonseed fatty cent of MD, and not exceeding 70 Weight percent of MP. ac1ds are prepared from saponified and acidulated cotton- (R f r s on foll i page) References Cited by the Examiner UNITED STATES PATENTS Magne et a1 260-304 Magne et a1 260-30.4 Dupuy et a1. 260--247 7 Rogier 260-247 7 14 OTHER REFERENCES Magne et a1.: Some N-Disubstituted Amides of Long- Chain Fatty Acids as Vinyl Plasticizers; Industrial and Engineering Chemistry; vol. 50, pages 617-618; 1958. MORRIS LIEBMAN, Primary Examiner.

L. T. JACOBS, Assistant Examiner. 

1. A PLASTIC COMPOSITION CONSISTING ESSENTIALLY OF A MIXTURE CONTAINING A VINYL CHLORIDE POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYVINYL CHLORIDE AND A VINYL CHLORIDE-VINYL ACETATE COPOLYMER WHICH CONTAINS A PREDOMINANT AMOUNT OF VINYL CHLOFIDE, AND FROM 10% TO 70% BY WEIGHT BASED ON THE WEIGHT OF THE POLYMER OF A PLASTICIZER COMPRISING A MIXTURE OF MORPHOLIDES OF DIMERIZED LONG CHAIN FATTY ACIDS WHICH ACIDS CONSIST ESSENTIALLY OF DIBASIC ACIDS CONTAINING FROM 32-44 CARBON ATOMS AND WHICH DIBASIC ACIDS RESULT FROM THE DIMERIZATION OF C16 TO C22 UNSATURATED FATTY ACIDS. 